DE3330004A1 - Process for the production of bipolar membranes - Google Patents
Process for the production of bipolar membranesInfo
- Publication number
- DE3330004A1 DE3330004A1 DE19833330004 DE3330004A DE3330004A1 DE 3330004 A1 DE3330004 A1 DE 3330004A1 DE 19833330004 DE19833330004 DE 19833330004 DE 3330004 A DE3330004 A DE 3330004A DE 3330004 A1 DE3330004 A1 DE 3330004A1
- Authority
- DE
- Germany
- Prior art keywords
- exchange membrane
- membrane
- produced
- bipolar
- bipolar membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title abstract description 8
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 238000005341 cation exchange Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000003014 ion exchange membrane Substances 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims 4
- 239000002243 precursor Substances 0.000 claims 4
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims 2
- 239000003011 anion exchange membrane Substances 0.000 claims 2
- 229920005601 base polymer Polymers 0.000 claims 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 125000000129 anionic group Chemical group 0.000 claims 1
- 150000001450 anions Chemical class 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 125000005270 trialkylamine group Chemical group 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/445—Ion-selective electrodialysis with bipolar membranes; Water splitting
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2275—Heterogeneous membranes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Urology & Nephrology (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
VERFAHREN ZUR HERSTELLUNG VON BIPOLAREN MEMBRANEN _ 3330004METHOD OF MANUFACTURING BIPOLAR MEMBRANES _ 3330004
Bipolare Membranen wurden hergestellt,um' mit dem Verfahren der Elektrolyse aus Neutralsalzen Säuren und Laugen herzustellen.Die bis dato verwendeten bip.olaren Elektroden sollten ersetzt werden,um die Elektrodenreaktionen durch eine elektrodialytische Wasserspaltung in der bipolaren Membranen zu ersetzen.Dadurch konnte das Verfahren vereinfacht und kostengünstiger gestaltet werden.Darüberhinaus gewinnen solche Verfahren an Interesse,da hierdurch anfallende salzhaltige Abwässer sinnvoll in widerverwendbare Produkte überführt werden können.Bipolar membranes were made to 'use the process of electrolysis to produce acids and alkalis from neutral salts, which have been used up to now bip.olar electrodes should be replaced to prevent electrode reactions replace it with electrodialytic water splitting in the bipolar membrane. This simplified the process and In addition, such processes are beneficial of interest, since the resulting salty wastewater makes sense can be converted into reusable products.
/D Die meisten in der Literatur beschriebenen bipolaren Membranen schei-^ terten an den hohen Ansprüchen,die an sie gestellt wurden. / D Most of the bipolar membranes described in the literature failed because of the high demands placed on them.
1. Ausreichende mechanische Stabilität1. Sufficient mechanical stability
2. die Fähigkeit bei hohen Stromdichten zu arbeiten2. the ability to work at high current densities
3. hohe Permselektivität3. high permselectivity
4. niedriger Widerstand4. Low resistance
5· hohe chemische Stabilität5 · high chemical stability
Außerdem sollte die bipolare Membran leicht herstellbar und reproduzier- \ bar sein.In addition, the bipolar membrane easily producible and reproducible \ should be cash.
Die bereits in der Literatur beschriebenen Verfahren beruhen entweder Lo auf Zusammenschmelzen von Kationen und anionenaustauschermembranen,so beschrieben im US-PS 3 372 101 und GB-PS 1 038 777 ,oder durch unterschiedliche Funktionalisierung auf den einzelnen Seiten der Membran, siehe US-PS 3 654 125 und Jap-PS γα $6, S>2-" .Darüberhinaus sind Verfahren zur Beschichtung von Ionenaustauschermembranen mit entgegengesetzt ^e^adifte-(^ Ionenaustauscherharzsuspensionen beschrieben (DE 2 737 l]fl Al).Das Problem der gegenseitigen Durchdringung wurde durch Verwendung von vernetzten Anionenaustauscherharzen gelöst. Das erfindungsgemäße Verfahren zur Herstellung von bipolaren Membranen ermöglicht die Vervendung von löslichen,unvernetzten lonenaustauscher- zo polymeren.Außerdem bestehen beide Schichten aus jeweils homogenen FoIymeren.Nach der vorliegenden Erfindungnk~ahn eine Kationenaustauschermembran aus sulfonierten! Polyethersulfon nach ihrer Herstellung sofort mit einer Polymergießlösung beschichtet werden,aus der das Lösungsmittel verdampft und anschließend in eine homogene Anionenaustauschermembran überführt wird.Die sich auf den Widerstand der bipolaren Membran negativ auswirkende Durchdringung der zwei Polymere/2 wird auf zwei Wegen unterdrückt:The procedure already described in the literature are based either Lo on fusion of cation and anion exchange, as described in US-PS 3,372,101 and GB-PS 1,038,777, or by different functionalization on the individual sides of the membrane, see U.S. Patent No. 3 654 125 and Jap-PS γα $ 6, S> 2- ". In addition, processes for coating ion exchange membranes with opposing ^ e ^ adifte - (^ ion exchange resin suspensions are described (DE 2 737 l] fl Al). The problem of mutual penetration was through use released from crosslinked anion exchange resins. the method according to the invention for the production of bipolar membranes makes it possible to Vervendung of soluble, non-crosslinked ion exchanger zo polymeren.Außerdem consist both layers of each of the present homogeneous FoIymeren.Nach Erfindungnk ~ ahn a cation exchange membrane made of sulfonated! polyethersulfone after their production be immediately with a polymer casting solution The penetration of the two polymers / 2, which has a negative effect on the resistance of the bipolar membrane, is suppressed in two ways:
1. Die Kationenaustauscherschicht ist in dem Lösungsmittel des zweiten Polymeren nicht löslich.1. The cation exchange layer is not soluble in the solvent of the second polymer.
2. Das zweite Polymer ist beim Aufbringen noch nicht geladen 2. The second polymer is not yet charged when it is applied
so daß Coulomb'sehe Kräfte als zusätzlicher Antrieb bei ' der Vermischung ausgeschlossen werden können.so that Coulomb's forces provide an additional drive 'mixing can be excluded.
Das prinzip der vorliegenden Erfindung soll durch die folgenden Beispiele erläutert werden.The principle of the present invention is illustrated by the following examples explained.
Eine ausgedampfte Kationenaustauschermembran mit der Ionenaustauscherkapazität von 1.2 meq/g wird mit einer 10% Lösung von chlormethyliertem Polyethersulfon mit einem Chlormethylgruppengehalt von 1.2meq/g in ft> Chloroform beschichtet und das Lösungsmittel verdampft .Der Polymerfilm wird anschließend während 10 Stunden mit einer 45$ igen wässrigen Trimethylaminlösung umgesetzt.Die so entstandene Membran zeigt einen Widerstand von 4ü/cm .A fully evaporated cation exchange membrane having the ion exchange capacity of 1.2 meq / g is evaporated with a 10% solution of chloromethylated polyether having a chloromethyl group content of 1.2meq / g in ft> chloroform coated and the solvent .The polymer film is subsequently strength for 10 hours with a 45 $ aqueous trimethylamine solution implemented. The resulting membrane shows a resistance of 4μ / cm.
Ein stark durchlässiger lösungsmittelinerter Träger v,rird einseitig mit Kationenaustauschergießlösung beschichtet und das Lösungsmittel verdampft.Die andere Seite wird wie im Beispiel 1 mit anionenaustausche] schicht beschichtet.Eine s6--hergestellt'e Membran zeigt einen Widerstand von 8Ä /cm .A highly permeable lösungsmittelinerter carrier v, r ird coated on one side with Kationenaustauschergießlösung and the solvent verdampft.Die other side is as in Example 1 with layer anionenaustausche] beschichtet.Eine s6 - hergestellt'e membrane shows a resistance of 8A / cm.
Als weitere Beispiele lassen sich alle möglichen Kombinationen von verschiedenen Ionenaustauscherkapazitäten anführen.In den Grenzen von 0.8 und 1.8 meq/g schwanken die^Widerstände der daraus gewonnenen bipolaren Membranen zwischen iifl/cm undAll possible combinations of different ion exchange capacities. The ^ resistances of the obtained from this fluctuate within the limits of 0.8 and 1.8 meq / g bipolar membranes between iifl / cm and
Claims (7)
gleiche Grundpolymere aufweisen, insbesondere mit der folgenden wiederkehrenden Einheit:2. Bipolar membrane according to claim 1, characterized in that the two exchanger membranes
have the same base polymers, in particular with the following repeating unit:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833330004 DE3330004A1 (en) | 1983-08-19 | 1983-08-19 | Process for the production of bipolar membranes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833330004 DE3330004A1 (en) | 1983-08-19 | 1983-08-19 | Process for the production of bipolar membranes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE3330004A1 true DE3330004A1 (en) | 1985-02-28 |
Family
ID=6206975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19833330004 Withdrawn DE3330004A1 (en) | 1983-08-19 | 1983-08-19 | Process for the production of bipolar membranes |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE3330004A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4883573A (en) * | 1986-12-10 | 1989-11-28 | Basf Aktiengesellschaft | Removal of acid from cathodic electrocoating baths by electrodialysis |
| DE4026154A1 (en) * | 1990-08-17 | 1992-02-20 | Fraunhofer Ges Forschung | BIPOLAR MULTI-LAYER MEMBRANES |
| EP0504904A3 (en) * | 1991-03-20 | 1993-03-17 | Yeda Research And Development Company, Ltd. | A supported, mechanically stable bipolar membrane for electrodialysis |
| DE4211267A1 (en) * | 1992-04-03 | 1993-10-07 | Fraunhofer Ges Forschung | Bipolar membrane and process for its manufacture |
-
1983
- 1983-08-19 DE DE19833330004 patent/DE3330004A1/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4883573A (en) * | 1986-12-10 | 1989-11-28 | Basf Aktiengesellschaft | Removal of acid from cathodic electrocoating baths by electrodialysis |
| DE4026154A1 (en) * | 1990-08-17 | 1992-02-20 | Fraunhofer Ges Forschung | BIPOLAR MULTI-LAYER MEMBRANES |
| EP0504904A3 (en) * | 1991-03-20 | 1993-03-17 | Yeda Research And Development Company, Ltd. | A supported, mechanically stable bipolar membrane for electrodialysis |
| DE4211267A1 (en) * | 1992-04-03 | 1993-10-07 | Fraunhofer Ges Forschung | Bipolar membrane and process for its manufacture |
| EP0563851A3 (en) * | 1992-04-03 | 1995-10-18 | Fraunhofer Ges Forschung | Bipolar membrane and process for its preparation |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8141 | Disposal/no request for examination |